EP2663533A1

EP2663533A1 - Optimized process for treating waste via hydrothermal treatment

Info

Publication number: EP2663533A1
Application number: EP12700069.3A
Authority: EP
Inventors: François CANSELL
Original assignee: Innoveox
Current assignee: Innoveox
Priority date: 2011-01-12
Filing date: 2012-01-09
Publication date: 2013-11-20
Also published as: WO2012095391A1; MX2013008155A; CN103459330A; RU2587179C2; FR2970247A1; FR2970247B1; JP5948346B2; CN103459330B; MX336168B; BR112013017895A2; KR20140020854A; US9073769B2; RU2013137241A; US20140051903A1; JP2014503354A; CA2824476A1

Abstract

The present invention relates to a process for the hydrothermal oxidation of organic compounds, optionally with oxidizable inorganic compounds, contained in an aqueous effluent, in which said aqueous effluent is injected into a tubular reactor where the effluent is brought to a supercritical pressure and where the temperature of the effluent is gradually increased from its initial temperature up to a supercritical temperature, without intermediate temperature reduction, while introducing into said tubular reactor an amount of oxidizing agent sufficient to completely oxidize the organic compounds and optionally to at least partly oxidize oxidizable inorganic compounds, the oxidizing agent being introduced in a fractionated manner at several points located increasingly downstream of the reactor, and in which the composition and/or the concentration of organic compounds and/or of oxidizable inorganic compounds within the effluent to be treated varies with time, and, upstream of the tubular reactor where the oxidation is carried out, the TOD of the effluent to be treated is measured and it is monitored so that is has a value greater than 120 g/l and less than 250 g/l prior to its injection into the tubular reactor.

Description

Optimized process of waste treatment by hydrothermal treatment

The present invention relates to a hydrothermal oxidation process of waste contained in an aqueous effluent. The invention relates in particular to the treatment of aqueous effluents comprising organic waste and / or dissolved salts.

Multiple processes for the transformation of aqueous effluents of this type have been described, among which may be mentioned in particular those in which the effluent to be treated is placed in the presence of an oxidizing agent in so-called "hydrothermal" conditions, namely at temperatures and pressures such that the water exceeds its critical point (pressure greater than 221 bar (2.21 .10 ³ Pa) and temperature above 374 ° C), which leads to an oxidation of the waste. In the case of organic compounds, the treatment typically leads to oxidation in the form of simple compounds such as CO ₂ and H ₂ O. The salts of metals other than alkali and alkaline earth metals are typically converted into hydrides. ) metal oxides. A method of this type, which is particularly interesting, is described in WO 02/20414, which makes it possible to control the temperature rise produced during hydrothermal oxidation. In the process described in this document, the effluent is treated in a tubular reactor by introducing the oxidizing agent not all at once but progressively along the tubular reactor, into several injection points of more in addition downstream of the flow of the effluent, which makes it possible to progressively increase the temperature of the flow according to an increasing curve, from an initial non-supercritical temperature (for example of the order of ambient or higher) until at a supercritical temperature. This process, called "by multi-injection of the oxidizing agent" makes it possible to carry out the oxidation in a controlled manner, avoiding a too intense production of energy which would otherwise damage the walls of the reactor, and nevertheless in an efficient manner, in particular account in view of the fact that the rise in temperature is continuous and strictly increasing (which, among other things, has the advantage of not inducing the sudden drops in temperature that can be observed with processes where the temperature is back-controlled by additions of refrigerants, which are suitable for inhibiting the oxidation reaction by quenching phenomena).

Furthermore, a process has been described for hydrothermal oxidation of organic compounds such as oily waste, contained in an aqueous effluent, the aqueous effluent being injected into a tubular reactor, in the presence of an oxidizing agent, and brought to a pressure. and at a supercritical temperature. Initial COD of the aqueous effluent before introduction into the reactor is measured (J. Sanchez-Oncto et al, Proceedings of the European Meeting on Supercritical Fluids 2008).

An object of the present invention is thus to improve the process described in WO 02/20414, in particular so as to make it well adapted to an industrial implementation where the nature and the concentration of the effluents can vary to a very large extent at course of time.

For this purpose, the present invention proposes to modify the process of WO 02/20414 by analyzing the quantity of compounds to be treated in the effluent to be treated, and possibly other parameters such as the concentration of halide ions or salts, and adjusting, if necessary, these parameters upstream of the hydrothermal treatment reactor prior to the multi-injection oxidation.

More specifically, the subject of the present invention is a process for the hydrothermal oxidation of organic compounds contained in an aqueous effluent, optionally with oxidizable inorganic compounds, in which the said aqueous effluent is injected into a tubular reactor where it is carried. effluent at supercritical pressure (i.e. greater than 221 bar ie 2.21 .10 ³ Pa) and where the temperature of the effluent is gradually increased from its initial temperature to a supercritical temperature (above 374 ° C), designated by years intermediate temperature decrease during the evolution increasing until introducing into said tubular reactor an amount of oxidizing agent sufficient to completely oxidize the organic compounds and optionally to oxidize at least partially oxidizable inorganic compounds, the oxidizing agent being introduced fractionally at several points located more and more. downstream of the reactor,

characterized in that the composition and / or the concentration of the organic compounds and / or oxidizable inorganic compounds within the effluent to be treated varies with time, and in that, upstream of the tubular reactor where the oxidation is carried out the DTO of the effluent to be treated is measured and maintained, or adjusted if necessary, to a value of less than 250 g / l.

According to the invention, the DTO of the effluent to be treated is measured, maintained or adjusted if necessary, to a value greater than 120 g / l and less than 250 g / l, prior to its injection into the tubular reactor.

Advantageously, the DTO of the effluent to be treated is measured, maintained or adjusted if necessary to a value of between 130 and 240 g / l, preferably between 130 and 220 g / l, advantageously between 140 and 220 g / l, prior to its injection into the tubular reactor.

By "DTO" is meant here the total chemical oxygen demand of the effluent to be treated, expressed in mole / L, which corresponds to the total amount of oxygen (expressed in moles) required to carry out the complete oxidation of the compounds organic and inorganic oxidizable present within one liter of the effluent. This total chemical demand "DTO" takes into consideration all the oxidizable species present, namely both the organic compounds and, where appropriate, those of any oxidizable inorganic compounds. It differs from "COD" (chemical oxygen demand) which only takes into consideration organic species. DTO is equal to COD when oxidizable inorganic species are absent.

In the case where the effluent to be treated contains organic compounds only, excluding oxidizable inorganic compounds, the DTO of the effluent is preferably maintained or adjusted between 150 and 220 g / l before injection into the tubular reactor. . Conversely, when the effluent to be treated contains oxidizable inorganic compounds (especially oxidizable metal compounds), it is most often preferable for the DTO to be maintained or adjusted to a value equal to or below 220 g / L. more preferably between 120 and 200 g / l, more preferably above 120 g / l.

In general, it is most often interesting that the DTO of the effluent is maintained or adjusted between 150 and 200 g / L before injection into the tubular reactor.

The control of the DTO of the effluent to be treated below 250 g / L before its introduction into the tubular oxidation reactor, as produced according to the invention, has, among other things, the advantage of inhibit an excessive rise in the operating temperature of the reactor, which could otherwise lead to damage. Therefore, the implementation of the invention translates into undeniable advantages in terms of safety and durability of the equipment and therefore the cost of maintenance and maintenance.

Moreover, the control of the DTO in the abovementioned ranges allows an optimal treatment of the waste to be treated, the DTO being sufficiently weak to allow an effective and total or substantially total oxidation of the species to be treated (oxidizable organic and / or inorganic compounds ). In addition, the control of the DTO above 120 g / mol makes it possible to induce in the tubular oxidation reactor a operating temperature sufficient not to consume the oxidizing agent unnecessarily.

In other words, the implementation of the conditions of the present invention allows a particularly advantageous optimization of the safety, efficiency and costs of the waste treatment facility and its maintenance.

The measurement of the DTO of the effluent and, if necessary, the modification of this DTO can be carried out according to any means known per se. The measurement of the DTO can in particular be carried out using a conventional DTO-meter or DCO-meter, for example of the type described in standards NFEN1484, IS08254, EPA4151. It is particularly possible to use DCO / DTO analyzers of the type marketed by ANAEL.

The modulation of the DTO can be obtained:

- if the DTO measured upstream of the reactor is too high: by dilution, for example by eu or by another less concentrated effluent; and

- if the DTO measured upstream of the reactor is too low: by concentration, for example by addition of organic and / or inorganic waste or a more concentrated effluent in the effluent to be treated.

Typically, for the implementation of the present invention, it is implemented, upstream of the oxidation reactor, a device for analyzing and preparing the effluent to be treated which typically comprises, upstream to downstream:

an analysis zone (and possibly a storage zone) for the effluent to be treated, provided with means for analyzing the DTO of the effluent;

an adjustment zone of the DTO, provided with means for feeding the medium contained in the analysis zone, and means for diluting or concentrating the medium contained in the adjustment zone (typically, this zone of adjustment is a tank equipped with means for supplying water (for dilution) or waste or concentrated effluent (for concentration); and

means for feeding the adjusted medium into the adjustment zone towards the oxidation reactor. According to preferred embodiments which further improve the interest of the method, the method of the invention may have at least one of the additional characteristics described below:

Preferably, in addition to the control of the DTO, other parameters of the effluent to be treated can be measured and adjusted as necessary.

Thus, according to a specific embodiment, upstream of the tubular reactor where the oxidation is carried out, the halogen concentration in the effluent to be treated is measured and maintained, or adjusted if necessary, to a lower value. at 2 g / L and preferably less than 1 g / L. The limitation of the halogen content makes it possible, inter alia, to inhibit the deterioration of the reactor by corrosion, which, again, results in advantages in terms of safety and cost reduction.

If necessary, the measurement of the halogen concentration can typically be carried out according to the IS09562 standard for the halogen dosing of absorbable organic compounds (AOX) and by inductively coupled plasma mass spectroscopy (ICP-MS) analysis. Adjustment of the concentration may be carried out by diluting the effluent (by addition of water or other more diluted effluent).

According to another specific embodiment, compatible with the preceding one, upstream of the tubular reactor where the oxidation is carried out, the concentration of salts in the effluent to be treated is measured and maintained, or adjusted if necessary, at a value of less than 10 g / l and preferably less than 5 g / l.

This limitation of the salt content makes it possible, inter alia, to inhibit, or even completely avoid, the fouling phenomena of the tubular reactor.

If necessary, the measurement of the salt concentration can typically be carried out by measuring the ionic conductivity of the medium. Adjustment of the concentration can be done by diluting the effluent (again, by adding water or other more diluted effluent).

Regarding the oxidation reaction in the tubular reactor and its preferred embodiments, reference can be made to the application WO 02/20414 which details these aspects. The process of the invention is well adapted to the treatment of most aqueous effluents, in particular urban sludge and effluents from the basic and processing industries, particularly effluents from the agri-food, paper, chemical and pharmaceutical industries, refining, oil, mechanical, metallurgical, aeronautical and nuclear industries.

The invention will be further illustrated by the illustrative examples given below.

EXAMPLE 1 Evaluation of the Efficiency of the Process According to the Invention for the Treatment of a Waste Resulting from the Chemical Industry

To illustrate the interest of the method of the present invention, the hydrothermal oxidation of a waste was carried out by implementing the device described in WO 02/20414 under different conditions, described below. Embodiments 1 and 2 correspond to the implementation according to the invention and the following two are provided for comparison.

The waste treated is a waste product from the chemical industry containing only compounds based on the elements C, H and O (a mixture comprising essentially alkanes alcohols and organic acids of the fatty acid type). From this waste, an aqueous medium was made whose DTO was controlled and regulated upstream of the oxidation reactor, in order to obtain at the reactor inlet a value of DTO called "initial DTO" whose values are given below. The mixture was preheated at the reactor inlet and then injected into the reactor where multiple oxygen injection was performed at three points further downstream. The first injection raises the medium to a temperature T1, the second to a temperature T2 and the third to a temperature T3, according to an increasing temperature profile (without ever decreasing temperature). The DTO of the flow at the outlet of the reactor, called "final DTO", was measured.

♦ Embodiment 1: initial DTO = 180 g / l

Injection temperature: 250 ° C

T1 = 360 ° C

T2 = 450 ° C

T3 = 550 ° C

According to this illustrative embodiment of the present invention, effective waste conversion is obtained with a final DTO equal to 30 mg / l, with control of the rise in temperature.

♦ Embodiment 2: initial DTO = 140 g / l

Injection temperature: 340 ° C

T1 = 370 ° C

T2 = 450 ° C

T3 = 530 ° C According to this illustrative embodiment of the present invention, effective waste conversion is achieved with a final DTO of 10 mg / L, with control of temperature rise.

♦ Embodiment 3: initial DTO = 120 g / l

Injection temperature: 250 ° C

T1 = 340 ° C

T2 = 350 ° C

T3 = 365 ° C

According to this embodiment, where the DTO is lower than that recommended according to the invention, the final DTO is 25 g / 1 + - 5g / l, which is too high, and does not allow sufficient treatment of the waste. (DTO of rejection too high).

♦ Embodiment 4: initial DTO = 250 g / 1

Injection temperature: 250 ° C

T1 = 360 ° C

T2 = 450 ° C

T3 = 580 ° C

According to this embodiment, where the DTO is higher than that recommended according to the invention, the final DTO is 65 g / l + - 5g / l, which is too high. The embodiment at a DTO of 250 g / L also corresponds to a limit at which the temperature becomes too high, inducing a risk of deterioration of the reactor.

EXAMPLE 2 Evaluation of the Efficiency of the Process According to the Invention for the Treatment of a Waste From a Distillery

Treated waste is a waste from a distillery made up of alcoholic drifts and drifts of sugars mainly. From this waste, an aqueous medium was made whose DTO was controlled and regulated upstream of the oxidation reactor, in order to obtain at the reactor inlet a value of DTO called "initial DTO" whose value is given below. The mixture was preheated at the reactor inlet and then injected into the reactor where multiple oxygen injection was performed at three points further downstream. The first injection raises the medium to a temperature T1, the second at a temperature T2 and the third at a temperature T3, according to an increasing temperature profile (without ever decreasing temperature). The DTO of the flow at the outlet of the reactor, called "final DTO", was measured. Initial DTO: 220 g / 1

Injection temperature: 200 ° C

T1 = 370 ° C

T2 = 450 ° C

T3 = 570 ° C

According to this illustrative embodiment of the present invention, effective waste conversion is achieved with a final DTO of 100 mg / l, with control of the temperature rise.

Claims

1. - Hydrothermal oxidation process of organic compounds contained in an aqueous effluent, optionally with oxidizable inorganic compounds, wherein said aqueous effluent is injected into a tubular reactor where the effluent is brought to a supercritical pressure and where the temperature the effluent is progressively increased from its initial temperature to a supercritical temperature, designated by the formula, without intermediate temperature decrease during the increasing evolution to infinity, by introducing into said tubular reactor a quantity of agent oxidizing agent sufficient to completely oxidize the organic compounds and optionally to oxidize at least partly oxidizable inorganic compounds, the oxidizing agent being fractionally introduced at several points situated further and further downstream of the reactor,

characterized in that the composition and / or the concentration of the organic compounds and / or oxidizable inorganic compounds within the effluent to be treated varies with time, and in that, upstream of the tubular reactor where the oxidation is carried out the DTO of the effluent to be treated is measured and maintained, or adjusted if necessary, to a value greater than 120 g / l and less than 250 g / l prior to injection into the tubular reactor.

2. - Process according to claim 1, wherein upstream of the tubular reactor where the oxidation is carried out, the DTO of the effluent to be treated is measured and maintained, or adjusted if necessary, to a value between 130 and 240 g / l, preferably between 130 and 220 g / l, advantageously between 140 and 220 g / l, prior to injection into the tubular reactor.

3. - Process according to claim 1 or 2, wherein the effluent to be treated contains organic compounds only, excluding oxidizable inorganic compounds, and where the DTO of the effluent is maintained or adjusted between 150 and 220g / L before injection into the tubular reactor.

4. - Process according to claim 1 or 2, wherein the effluent to be treated contains oxidizable inorganic compounds, and where the DTO of the effluent is maintained or adjusted to a value greater than 120 g / l and less than or equal to 220 g / L, before injection into the tubular reactor.

5. - Method according to one of claims 1 to 4, wherein the DTO of the effluent is maintained or adjusted between 150 and 200g / L before injection into the tubular reactor.

6. - Method according to one of claims 1 to 5, which is implemented, upstream of the oxidation reactor, a device for analyzing and preparing the effluent to be treated which typically comprises, upstream in downstream :

an analysis zone of the effluent to be treated, provided with means for analyzing the DTO of the effluent;

an adjustment zone of the DTO, provided with means for feeding the medium contained in the analysis zone, and means making it possible to dilute or concentrate the medium contained in the adjustment zone; and

means for feeding the adjusted medium into the adjustment zone towards the oxidation reactor.

7. - Method according to one of claims 1 to 6, wherein upstream of the tubular reactor where the oxidation is performed, the halogen concentration in the effluent to be treated is measured and maintained, or adjusted if less than 2 g / L and preferably less than 1 g / L.

8. - Method according to one of claims 1 to 7, wherein upstream of the tubular reactor where the oxidation is carried out, the salt concentration in the effluent to be treated is measured and maintained, or adjusted if less than 10 g / L and preferably less than 5 g / L.

9. - Method according to one of claims 1 to 6, wherein the treated effluent is an aqueous effluent selected from urban sludge and effluents from the basic and processing industries, particularly effluents from the agro-food industry, paper mills chemical, pharmaceutical, refining, petroleum, mechanical, metallurgical, aeronautical or nuclear.